Problems associated with the formation and discharge of electrostatic charge during the manufacture and utilization of photographic film and paper have been recognized for many years by the photographic industry. The accumulation of charge on film or paper surfaces leads to the attraction of dust, which can produce physical defects. The discharge of accumulated charge during or after the application of the sensitized emulsion layer(s) can produce irregular fog patterns or "static marks" in the emulsion. The severity of static problems has been exacerbated greatly by increases in the sensitivity of new emulsions, increases in coating machine speeds, and increases in post-coating drying efficiency. The charge generated during the coating process results primarily from the tendency of webs of high dielectric polymeric film base to charge during winding and unwinding operations (unwinding static), during transport through the coating machines (transport static), and during post-coating operations such as slitting and spooling. Static charge can also be generated during the use of the finished photographic film product. In an automatic camera, the winding of roll film out of and back into the film cassette, especially in a low relative humidity environment, can result in static charging. Similarly, high-speed automated film processing can result in static charge generation. Sheet films are especially subject to static charging during removal from light-tight packaging (e.g., x-ray films).
It is generally known that electrostatic charge can be dissipated effectively by incorporating one or more electrically-conductive "antistatic" layers into the film structure. Antistatic layers can be applied to one or to both sides of the film base as subbing layers either beneath or on the side opposite to the light-sensitive silver halide emulsion layers. An antistatic layer can alternatively be applied as an outer-coated layer either over the emulsion layers or on the side of the film base opposite to the emulsion layers or both. For some applications, the antistatic agent can be incorporated into the emulsion layers. Alternatively, the antistatic agent can be directly incorporated into the film base itself.
A wide variety of electrically conductive materials can be incorporated into antistatic layers to produce a wide range of conductivities. Most of the traditional antistatic systems for photographic applications employ ionic conductors. Charge is transferred in ionic conductors by the bulk diffusion of charged species through an electrolyte. Antistatic layers containing simple inorganic salts, alkali metal salts of surfactants, ionic conductive polymers, polymeric electrolytes containing alkali metal salts, and colloidal metal oxide sols (stabilized by metal salts) have been described previously. The conductivities of these ionic conductors are typically strongly dependent on the temperature and relative humidity in their environment. At low humidities and temperatures, the diffusional mobilities of the ions are greatly reduced and conductivity is substantially decreased. At high humidities, antistatic back-coatings often absorb water, swell, and soften. In roll film, this results in adhesion of the back-coating to the emulsion side of the film. Also, many of the inorganic salts, polymeric electrolytes, and low molecular weight surfactants used are water-soluble and are leached out of the antistatic layers during processing, resulting in a loss of antistatic function.
Antistatic systems employing electronic conductors have also been described. Because the conductivity depends predominantly on electronic mobilities rather than ionic mobilitics, the observed electronic conductivity is independent of relative humidity and only slightly influenced by the ambient temperature. Antistatic layers have been described which contain conjugated polymers, conductive carbon particles, or semi-conductive inorganic particles.
Trevoy (U.S. Pat. No. 3,245,833) has taught the preparation of conductive coatings containing semi-conductive silver or copper iodide dispersed as particles less than 0.1 .mu.m in size in an insulating film-forming binder, exhibiting a surface resistance of 10.sup.2 to 10.sup.11 ohms per square. The conductivity of these coatings is substantially independent of relative humidity. Also, the coatings are relatively clear and sufficiently transparent to permit their use as antistatic coatings for photographic film. However, if a coating containing copper or silver iodides was used as a subbing layer on the same side of the film base as the emulsion, Trevoy found (U.S. Pat. No. 3,428,451) that it was necessary to overcoat the conductive layer with a dielectric, water-impermeable barrier layer to prevent migration of semi-conductive salt into the silver halide emulsion layer during processing. Without the barrier layer, the semi-conductive salt could interact deleteriously with the silver halide layer to form fog and a loss of emulsion sensitivity. Also, without a barrier layer, the semi-conductive salts are solubilized by processing solutions, resulting in a loss of antistatic function.
Another semi-conductive material has been disclosed by Nakagiri and Inayama (U.S. Pat. No. 4,078,935) as being useful in antistatic layers for photographic applications. Transparent, binderless, electrically semi-conductive metal oxide thin films were formed by oxidation of thin metal films, which had been vapor deposited onto film base. Suitable transition metals include titanium, zirconium, vanadium, and niobium. The microstructure of the thin metal oxide films is revealed to be non-uniform and discontinuous, with an "island" structure almost "particulate" in nature. The surface resistivity of such semi-conductive metal oxide thin films is independent of relative humidity and reported to range from 10.sup.5 to 10.sup.9 ohms per square. However, the metal oxide thin films are unsuitable for photographic applications since the overall process used to prepare these thin films is complicated and costly, abrasion resistance of these thin films is low, and adhesion of these thin films to the base is poor.
A highly effective antistatic layer, incorporating an "amorphous" semi-conductive metal oxide, has been disclosed by Guestaux (U.S. Pat. No. 4,203,769). The antistatic layer is prepared by coating an aqueous solution containing a colloidal gel of vanadium pentoxide onto a film base. The colloidal vanadium pentoxide gel typically consists of entangled, high aspect ratio, flat ribbons 50-100 .ANG. wide, about 10 .ANG. thick, and 1,000-10,000 .ANG. long. These ribbons stack flat in the direction perpendicular to the surface when the gel is coated onto the film base. This results in electrical conductivities for thin films of vanadium pentoxide gels (about 1 .OMEGA..sup.-1 cm.sup.-1), which are typically about three orders of magnitude greater than is observed for similar thickness films containing crystalline vanadium pentoxide particles. In addition, low surface resistivities can be obtained with very low vanadium pentoxide coverages. This results in low optical absorption and scattering losses. Also, the thin films are highly adherent to appropriately prepared film bases. However, vanadium pentoxide is soluble at high pH and must be overcoated with a non-permeable, hydrophobic barrier layer in order to survive processing. When used with a conductive subbing layer, the barrier layer must be coated with a hydrophilic layer to promote adhesion to emulsion layers above. (See Anderson et al, U.S. Pat. No. 5,006,451)
Conductive fine particles of crystalline metal oxides dispersed with a polymeric binder have been used to prepare optically transparent, humidity insensitive, antistatic layers for various imaging applications. Many different metal oxides--such as ZnO, TiO.sub.2, ZrO.sub.2, SnO.sub.2, Al.sub.2 O.sub.3, In.sub.2 O.sub.3, SiO.sub.2, MgO, BaO, MoO.sub.3 and V.sub.2 O.sub.5 --are alleged to be useful as antistatic agents in photographic elements or as conductive agents in electrostatographic elements in such patents as U.S. Pat. Nos. 4,275,103; 4,394,441; 4,416,963; 4,418,141; 4,431,764; 4,495,276; 4,571,361; 4,999,276; and 5,122,445. However, many of these oxides do not provide acceptable performance characteristics in these demanding environments. Preferred metal oxides are antimony doped tin oxide, aluminum doped zinc oxide, and niobium doped titanium oxide. Surface resistivities are reported to range from 10.sup.6 -10.sup.9 ohms per square for antistatic layers containing the preferred metal oxides. In order to obtain high electrical conductivity, a relatively large amount (0.05-10 g/m.sup.2) of metal oxide must be included in the antistatic layer. This results in decreased optical transparency for thick antistatic coatings. The high values of refractive index (&gt;2.0) of the preferred metal oxides necessitates that the metal oxides be dispersed in the form of ultrafine (&lt;0.1 .mu.m) particles in order to minimize light scattering (haze) by the antistatic layer.
Antistatic layers comprising electro-conductive ceramic particles, such as particles of TiN, NbB.sub.2, TiC, LaB.sub.6 or MoB, dispersed in a binder such as a water-soluble polymer or solvent-soluble resin are described in Japanese Kokai No. 4/55492, published Feb. 24, 1992.
Fibrous conductive powders comprising antimony-doped tin oxide coated onto non-conductive potassium titanate whiskers have been used to prepare conductive layers for photographic and electrographic applications. Such materials are disclosed, for example, in U.S. Pat. Nos. 4,845,369 and 5,116,666. Layers containing these conductive whiskers dispersed in a binder reportedly provide improved conductivity at lower volumetric concentrations than other conductive fine particles as a result of their higher aspect ratio. However, the benefits obtained as a result of the reduced volume percentage requirements are offset by the fact that these materials are relatively large in size such as 10 to 20 .mu.m in length, and such large size results in increased light scattering and hazy coatings.
Use of a high volume percentage of conductive fine particles in an electro-conductive coating to achieve effective antistatic performance results in reduced transparency due to scattering losses and in the formation of brittle layers that are subject to cracking and exhibit poor adherence to the support material. It is thus apparent that it is extremely difficult to obtain non-brittle, adherent, highly transparent, colorless electro-conductive coatings with humidity-independent process-surviving antistatic performance.
The requirements for antistatic layers in silver halide photographic films are especially demanding because of the stringent optical requirements. Other types of imaging elements such as photographic papers and thermal imaging elements also frequently require the use of an antistatic layer but, generally speaking, these imaging elements have less stringent requirements.
A specific example of electrically-conductive layers which are especially advantageous for use in imaging elements and are capable of effectively meeting the stringent optical requirements of silver halide photographic elements are layers comprising a dispersion in a film-forming binder of fine particles of an electronically-conductive metal antimonate as described in Christian et al U.S. Pat. No. 5,368,995 issued Nov. 29, 1994. For use in imaging elements, the average particle size of the electronically conductive metal antimonate is preferably less than about one .mu.m and more preferably less than about 0.5 .mu.m. For use in imaging elements where a high degree of transparency is important, it is preferred to use colloidal particles of an electronically-conductive metal antimonate, which typically have an average particle size in the range of 0.01 to 0.05 .mu.m. The preferred metal antimonates have rutile or rutile-related crystallographic structures and are represented by either Formula (I) or Formula (II) below: EQU M.sup.+2 Sb.sup.+5.sub.2 O.sub.6 wherein M.sup.+2 =Zn.sup.+2, Ni.sup.+2, Mg.sup.+2, Fe.sup.+2, Cu.sup.+2, Mn.sup.+2, Co.sup.+2 (I) EQU M.sup.+3 Sb.sup.+5 O.sub.4 where M.sup.+3 =In.sup.30 3, Al.sup.+3, Sc.sup.+3, Cr.sup.+3, Fe.sup.+3, Ga.sup.+3 (II)
Electrically conductive layers are also commonly used in imaging elements for purposes other than providing static protection. Thus, for example, in electrostatographic imaging it is well known to utilize imaging elements comprising a support, an electrically conductive layer that serves as an electrode, and a photoconductive layer that serves as the image-forming layer. Electrically-conductive agents utilized as antistatic agents in photographic silver halide imaging elements are often also useful in the electrode layer of electrostatographic imaging elements.
As indicated above, the prior art on electrically-conductive layers in imaging elements is extensive, and a very wide variety of different materials have been proposed for use as the electrically-conductive agent. There is still, however, a critical need in the art for improved electrically conductive layers which are useful in a wide variety of imaging elements, which can be manufactured at reasonable cost, which are resistant to the effects of humidity change, which are durable and abrasion-resistant, which are effective at low coverage, which are adaptable to use with transparent imaging elements, which do not exhibit adverse sensitometric or photographic effects, and which are substantially insoluble in solutions with which the imaging element typically comes in contact, for example, the aqueous alkaline developing solutions used to process silver halide photographic films.
Many imaging elements of the type hereinabove described include one or more layers which contain gelatin. Thus, the electrically conductive layer is commonly in adhering contact with a layer containing gelatin. Examples of photographic elements of such structure include elements in which the electrically-conductive layer is a subbing layer underlying a gelatin silver halide emulsion layer or a gelatin-containing anticurl layer, elements in which the electrically-conductive layer is an overcoat layer overlying a gelatin silver halide emulsion layer, and elements in which the electrically-conductive layer is an outermost layer overlying a gelatin-containing anticurl layer on the side of the support opposite to the silver halide emulsion layer.
It is extremely difficult to get adequate adhesion between an electrically conductive layer, which comprises a high concentration of electrically conductive metal-containing particles and a gelatin-containing layer, which is in adhering contact therewith. A major factor contributing to the adhesion problem is that the volumetric ratio of electrically-conductive metal-containing particles to binder in the electrically-conductive layer must usually be quite high in order to get the high level of electrical conductivity that is desired. For example, the electrically conductive metal-containing particles typically constitute 20 to 80 or more volume percent of the electrically conductive layer. As a result of too small an amount of binder being present in the electrically conductive layer, there can be a serious problem of inadequate adhesion to gelatin-containing layers that are in adhering contact therewith. This problem is solved by Lelental et al U.S. Pat. No. 5,508,135 by addition of a particular polyelectrolyte to the electrically conductive layer.
It is toward the objective of providing an improved electrically conductive layer, which is highly conductive and highly transparent and which is an integral part of the photographic support, that the present invention is directed.